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The effect of the size of gold particles deposited on CeO 2 and TiO 2 supports on their catalytic behavior in the aerobic oxidation of benzyl alcohol in different solvents (mesitylene, toluene, and supercritical carbon dioxide) has been investigated. The size of supported gold particles deposited via a colloidal route was in the range 1.3-11.3 nm, as determined by means of EXAFS and HAADF-STEM measurements. The catalytic performance of the supported gold catalysts in the different solvents revealed a significant effect of the gold particle size. Optimal activity was observed for catalysts with medium particle size (ca. 6.9 nm) whereas smaller and bigger particles showed inferior activity. Identical trends for the activity-particle size relationship were found using Au/CeO 2 and Au/TiO 2 for the reaction at atmospheric pressure in conventional solvents (mesitylene, toluene) as well as under supercritical conditions (scCO 2 ). Selectivity to benzaldehyde was only weakly affected by the gold particle size and mainly depended on reaction conditions. In supercritical CO 2 (scCO 2 ) selectivity was higher than in the conventional solvents under atmospheric pressure. All catalysts tested with particle sizes ranging from 1.3 to 11.3 nm showed excellent selectivity of 99% or higher under supercritical conditions.

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